N-nitrosodiphenylamine (NDPhA) is a disinfection byproduct (DBP) in drinking water. However, it is not known what governs the formation of NDPhA and which precursor(s) in the raw water is responsible for its formation. We report here diphenylamine (DPhA) as a key precursor of NDPhA, and we describe the effect of water pH and chloramination conditions on the formation of NDPhA. To identify precursors of NDPhA, raw water samples were collected from the same drinking water system in which NDPhA was previously detected. Analysis of the raw water samples showed the presence of 1.3 ng/L of DPhA and no detectable NDPhA. Seven hours after the treatment of the raw water with chloramines, the concentration of DPhA decreased to 0.4 ng/L with corresponding formation of NDPhA (0.4 ng/L). Controlled experiments involving chloramination of DPhA in water showed that chloramines were essential to the formation of NDPhA, and that increasing the pH from 4 to 10 resulted in 64-fold enhancement in NDPhA formation. Removal of DPhA and formation of NDPhA was found by mass imbalance, which led to the identification of two new DBPs, phenazine (MW 180 Da) and a chlorinated phenazine derivative (MW 216 Da), using liquid chromatography tandem mass spectrometry and gas chromatography mass spectrometry. Both new DBPs were detected only in the treated water and not in the raw water. Phenazine and N-chlorophenazine have never been reported as DBPs and neither their occurrence in drinking water nor their health effects are known.